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 Free-Energy Change
Gibbs free energy “∆G”
More –ve energy, more tendency for the
reaction to go
 Mg + H2O (l) + ½O2 → Mg(OH)2 (s) ∆Go = -142,600 cal
On the other hand
 Cu + H2O (l) + ½O2 → Cu(OH)2 (s) ∆Go = -28,600 cal
For the reaction
 Au + 3/2H2O (l) + 3/2O2 → Au(OH)3 (s) ∆Go = +15,700 cal
 Free energy is positive; no tendency for reaction

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• ∆G = - nFE
• Greater the E, greater is the
tendency for reaction.
• Tendency to corrode is not a
measure of reaction rate

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The EMF and Galvanic Series

• EMF Series is an orderly arrangement of

standard potentials for all metals.

• It has only limited utility for predicting which

metal is anodic to another.

• In practice, the actual activities of ions in

eqm with a given metal, vary greatly with the
environment.
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EMF Series has limitation in predicting the
galvanic effects in a particular environment.

For this reason Galvanic series has been

formulated.

It reveals an arrangement of metals and

alloys in accord with their actual measured
potentials in a given environment.
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The damage incurred by coupling of two metals
depends on:

•How far apart they are in Galvanic series

•Their relative areas
•Extent to which they are polarized

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 Reference Half-Cells

Electrodes with fixed potential values regardless of

electrolyte.

1. Calomel Half-Cell

Mercury in eqm with Hg22+ ions; the activity is

determined by the solubility of Hg2Cl2 (mercurous
chloride or calomel)
Hg2Cl2 + 2e- → 2Hg + 2Cl- o = 0.268 V

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2. Silver-Silver Chloride Half-Cell
When the electrode is immersed in chloride solution
AgCl + e → Ag + Cl- o = 0.222 V

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3. Saturated Copper-Copper Sulfate Half-Cell

Metallic copper immersed in saturated copper sulfate

Used in field measurements; e.g. soil-pipeline potential

The half-cell reaction is

Cu2+ + 2e → Cu o = 0.337 V

For standard copper sulfate, the potential is 0.316 V

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 Measuring the Corrosion Potential
• The potential of a corroding metal, often termed Ecorr, is
probably the single most useful variable measured in
corrosion studies or for corrosion monitoring.
• It is readily measured by determining the voltage
difference between a metal in its environment and
an appropriate reference electrode using a high
impedance voltmeter.
• The reference electrode is contained in a Luggin
capillary to prevent any contamination of the reference
electrode by the environment or the opposite, that is,
leaking some corrosive agent in the environment
being monitored, while making potential measurements
very close to the surface of the metal being monitored.

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• In measuring and reporting corrosion potentials, it is
necessary to indicate the magnitude of the voltage and its
sign. In the example shown in Fig. 4.7, the corrosion
potential of metal M is −0.405 V.
• The minus sign indicates that the metal is negative with
respect to the reference electrode. However, if the metal was
connected to the low point (Lo) and the reference
electrode to the high point (Hi) the reading would be
+0.405 V.
• It is customary to connect the reference electrode to the
low point or the instrumental ground to avoid any confusion
in reporting. Nonetheless, some manufacturers of
electrochemical equipment have done the opposite.

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 Potential-pH Diagram
• The stability of a metal when exposed to a given
environment depends on a multitude of factors that may
vary greatly with the pH and oxidizing or reducing power
of that environment.
• One useful concept to represent the effects of aqueous
environments on metals became known as potential-pH
(E-pH) diagrams, also called predominance or Pourbaix
diagrams, which have been adopted universally since
their introduction in late 1940s.
• Some interesting uses of such diagrams are:
1. predict whether or not corrosion can occur;
2. estimate the composition of the corrosion products formed; and
3. predict environmental changes which will prevent or reduce corrosion
attack.

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• The chemical behavior of water across all
possible values of potential and pH as shown in
Fig. 4.10 is divided into three regions.
– In the upper region, water can be oxidized to produce
oxygen while in the lower region it can be
reduced to form hydrogen gas.
• Water is therefore only thermodynamically
stable between lines (a) and (b).
• It is common practice to superimpose
these two lines (a) and (b) on all E-pH
diagrams to mark the water stability
boundaries.
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• A metal is deemed to be in corroding condition
when the concentration of its ions in the solution
≥ 10-6 M.
• If the concentration of ions is less than this
value, the metal is in a condition of immunity.

• Three possible states of metallic materials are:

1. Immunity region: In this region a metal is
considered to be totally immune from corrosion
attack and safe to use. Cathodic protection may be
used to bring the potential of a metal closer to that
region by forcing a cathodic shift.

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2. Passive region: In such region a metal tends to
become coated with an oxide or hydroxide that may
form on the metal either as a compact and
adherent film practically preventing all direct
contact between the metal itself and the
environment, or as a porous deposit which only
partially prevents contact between the metal and the
environment.
3. Corrosion region: Thermodynamic calculations
indicate that, in such region of an E-pH diagram, a
metal is stable as an ionic (soluble) product and
therefore susceptible to corrosion attack. Experience
is required to find out the extent and form of the
corrosion attack that may occur in the corrosion
region(s) of a Pourbaix diagram.
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